Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0041—Digital printing on surfaces other than ordinary paper
  • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0072—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using mechanical wave energy, e.g. ultrasonics; using magnetic or electric fields, e.g. electric discharge, plasma
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
  • Y10T428/24372—Particulate matter
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
  • Y10T428/24372—Particulate matter
  • Y10T428/24405—Polymer or resin [e.g., natural or synthetic rubber, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249987—With nonvoid component of specified composition
  • Y10T428/249991—Synthetic resin or natural rubbers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/254—Polymeric or resinous material
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2848—Three or more layers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

• the present invention relates to a thermoplastic resin film excellent in ink adhesion and scratch resistance in printed matter of an oxidation polymerization type ink and an ultraviolet curing type ink. Background technology>
• thermoplastic resin films such as polyethylene, polypropylene, and polyethylene terephthalate films are used.
• white polyolefin-based synthetic paper with improved printability can be used for printing such as gravure, flexo, letterpress, and offset, and can provide expressive printed matter.
• Such polyolefin-based synthetic papers are usually subjected to an appropriate surface treatment to impart printability such as ink transferability and ink adhesion, because the polyolefin-based resin as a raw material is non-polar.
• a method is known in which a resin film is subjected to an oxidation treatment and then a coating agent is applied.
• the oxidation treatment method methods such as corona discharge treatment and flame treatment are known.
• the coating agent for example, a coating agent such as a polyethyleneimine / ethyleneimine / ethylene urine copolymer is disclosed in JP-A-Heisei 01-141376, JP-A-Heisei 06-024. No. 47, and Japanese Patent Application Laid-Open No. 2000-29041.
• Polyolefin-based synthetic paper surface-treated in this way is easily scratched on its surface, and the ink peels off from the surface when the printed material is pulled in the processing steps such as cutting and bookbinding. There is a problem. If this ink is required to have anti-peeling properties (scratch resistance), it is necessary to use a friction-resistant ink during printing or to perform surface varnishing during or after the printing process. Very in comparison Has become expensive.
• An object of the present invention is to provide a thermoplastic resin film having an ink adhesiveness and a scratch resistance of a printed material in a printed material obtained by printing such as gravure, flexo, letter press, or offset. I do.
• thermoplastic resin film having the following constitution, a printed matter, and a label having an adhesive layer.
• curable resin ( ⁇ ) and olefin resin ( ⁇ ) whose pencil hardness is HB or more according to JIS—K_5600—5-4.
• the olefin resin ( ⁇ ) ) A thermoplastic resin film having a coating layer containing protrusions derived from at least one surface.
• thermoplastic resin film according to any one of the above items 1 to 2, which satisfies the following.
• thermoplastic resin film according to any one of the above items 1 to 3, wherein the curable resin (A) has an elongation of 300% or less in accordance with JIS-K-1 713.
• thermoplastic resin film c according to any one of 1 to 4 above, wherein the curable resin (A) is at least one of a thermosetting resin, an ultraviolet curable resin, and an electron beam curable resin.
• Curable resin Force Polyester acrylate resin, polyether acrylate resin, polyurethane acrylate resin, epoxy acrylate resin, (meth) acrylate resin, urea resin, phenol resin, Unsaturated polyester resin, epoxy resin, silicone resin, melamine resin, alk 6.
• Curable resin (A) 1 The thermoplastic resin film according to 6 above, which is a polyurethane resin.
• thermoplastic resin film according to any one of 1 to 8 above, wherein the minimum film forming temperature of the olefin resin (B) is 40 ° C or more.
• thermoplastic resin film according to any one of the above 1 to 9, wherein the weight average particle diameter d of the olefin resin (B) is 0.1 to 10 ⁇ .
• Olefin-based resin (II) Strength The thermoplastic resin film according to any one of 1 to 10 above, which comprises an olefinic copolymer to which at least one of a carboxylic acid and an anhydride thereof is bonded.
• thermoplastic resin film according to the above item 11 wherein the acid content of the olefin copolymer is 30% by weight or less.
• thermoplastic resin film according to any one of the above items 1 to 12, wherein the thermoplastic resin film contains at least one of an inorganic fine powder and an organic filler.
• thermoplastic resin film according to the above 13 wherein the content of at least one of the inorganic fine powder and the organic filler is 75% by weight or less.
• thermoplastic resin film according to any one of the above 1 to 14, wherein the thermoplastic resin film has a multilayer structure.
• thermoplastic resin film according to any one of 1 to 15 above, wherein the thermoplastic resin film is stretched in at least one direction.
• thermoplastic resin film according to any one of the above items 1 to 17.
• FIG. 1 is a schematic cross-sectional view schematically showing one example of a coating layer of the thermoplastic resin film of the present invention.
• the thermoplastic resin used as the raw material includes ethylene resins such as high-density polyethylene and medium-density polyethylene, propylene resins, polyolefins such as polymethyl-1-pentene resin and ethylene-monocyclic olefin copolymer. Resin, polyamide resin such as Nylon-6, Nylon-6,6, Nylon-6,10, Nylon-6,12, etc., heat of polyethylene terephthalate and its copolymer, polyethylene naphthalate, aliphatic polyester, etc.
• thermoplastic polyester resin polycarbonate, atactic polystyrene, syndiotactic polystyrene, polymethyl methacrylate, polychlorinated biel, polyvinylidene, ethylene-butyl acetate copolymer, polyphenylene sulfide, etc. Resins. These can be used in combination of two or more.
• thermoplastic resins in order to further exert the effects of the present invention, in order to further exert the effects of the present invention, it is necessary to use poly (ethylene terephthalate) or a copolymer thereof, as well as polypropylene, polystyrene, polymethyl-11-pentene resin, and ethylene-monocyclic copolymer. It is preferable to use a mixture of coalescing or the like or a non-polar polyolefin resin. That's right. Further, among the polyolefin-based resins, a propylene-based resin is preferable in terms of chemical resistance, cost, and the like.
• Such a propylene-based resin is mainly composed of propylene, which is a propylene homopolymer and is isotactic or syndiotactic, and has various stereoregularities, such as polypropylene and propylene.
• propylene which is a propylene homopolymer and is isotactic or syndiotactic, and has various stereoregularities, such as polypropylene and propylene.
• copolymers with olefins such as heptene-1,4-methinolepentene-11 are used.
• the copolymer may be a binary, ternary, or quaternary system, and may be a random copolymer or a block copolymer.
• a resin having a melting point lower than that of the propylene homopolymer such as polyethylene or ethylene / butyl acetate copolymer, is blended in an amount of 2 to 25% by weight to improve the stretchability. Is preferred.
• the thermoplastic resin film may have a two-layer structure or a multilayer structure of three or more layers, and the number of stretching axes of this multilayer structure is one axis Z l axis, one axis Z two axes, two axis Z l axis , 1 Axis / 1 Axis Z 2 Axis, 1 Axis Z 2 Axis 1 Axis, 2 Axis / 1 Axis No 1 Axis, 1 Axis Z 2 Axis / 2 Axis, 2 Axis Z 2 Axis / 1 Axis, 2 Axis Z 2 Axis Z-axis may be used.
• the type of the inorganic fine powder and the inorganic or organic filler contained in the thermoplastic resin film is not particularly limited.
• the inorganic fine powder examples include heavy calcium carbonate, light calcium carbonate, calcined sauce, tanolek, barium sulfate, diatomaceous earth, magnesium oxide, zinc oxide, titanium oxide, silicon oxide, and the like. It may be. Of these, heavy calcium carbonate, calcined clay, and talc are preferred because they are inexpensive and have good moldability.
• Organic fillers include polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, polystyrene, melamine resin, polyethylene sulphite, polyimide, polyethyl acrylate Melting point of terketone, polyether ether ketone, polyphenylene sulfide, poly 4-methyl-11-pentene, polymethyl methacrylate, homopolymer of cyclic olefin, copolymer of cyclic olefin and ethylene, etc. Is 120 to 300 ° C, or a glass transition temperature of 120 to 280 ° C.
• One of the above inorganic fine powders and / or organic fillers may be selected and used alone, or two or more may be used in combination.
• the content of the inorganic fine powder and / or the organic filler is 75% by weight or less, preferably 0.5 to 65% by weight, and more preferably 3 to 55% by weight.
• the amount of the inorganic fine powder and / or the organic filler contained in the single-layered or multi-layered base material layer of the thermoplastic resin film exceeds 75% by weight, it is performed after longitudinal stretching. Easy to do. If the amount of the inorganic fine powder and / or Z or organic filler contained in the surface layer of the multilayer structure exceeds 75% by weight, the surface strength of the surface layer after transverse stretching is low, and the surface layer breaks down when the printing ink is spread. Resulting in.
• the average particle diameter of the inorganic fine powder and the average dispersed particle diameter of the organic filler used in the present invention are preferably in the range of 0.01 to 20 / im, more preferably 0.05 to 15 / zm. Considering the easiness of mixing with a thermoplastic resin, it is preferable to use one having a particle size of 0.01 ⁇ or more.
• the particle diameter is less than 0.01 ⁇ , it is difficult to form pores by stretching, and a stretched film having a desired surface tends not to be obtained. On the other hand, if the particle diameter exceeds 20 / zm, the stretchability tends to decrease, and there is a tendency that stretch breaks and holes during molding are increased.
• stabilizers may be added.
• a stabilizer hindered phenol-based and phosphorus-based, 0. stabilizers amine such as 00 1-1 weight 0/0, as light stabilizers, sterically hindered Amin Ya downy Nzotoriazoru system, stable light such Benzofu enone system 0.001 to 1% by weight of a dispersing agent of an inorganic fine powder, for example, a silane coupling agent, a higher fatty acid such as oleic acid or stearic acid, metal stone, polyacrylic acid, polymethacrylic acid or a salt thereof. . 01-4% by weight.
• a dispersing agent of an inorganic fine powder for example, a silane coupling agent, a higher fatty acid such as oleic acid or stearic acid, metal stone, polyacrylic acid, polymethacrylic acid or a salt thereof. . 01-4% by weight.
• thermoplastic resin film is not particularly limited, and various known methods can be used. Specific examples include melting using a single-layer or multilayer T-die or I-die connected to a screw-type extruder. Casting, calendering, rolling, inflation molding, extruding resin into sheet form, removing solvent and oil after casting or calendering of a mixture of thermoplastic resin and organic solvent or oil, thermoplastic resin solution Forming a film by laminating at least one surface of a thermoplastic resin film—pulp paper, nonwoven fabric, or the like using a melt lamination or an adhesive.
• thermoplastic resins of the following types: longitudinal stretching using the peripheral speed difference between roll groups, horizontal stretching using a tenter oven, rolling, simultaneous biaxial by combining a tenter open and linear motor Stretching and the like can be mentioned, and two or more of these methods may be combined. Of these, sequential biaxial stretching, in which longitudinal stretching is performed and then transverse stretching is preferred.
• Specific examples of the production of the base material include: melt-kneading the resin composition for the base material layer in advance; extruding the same into a sheet form; stretching in the longitudinal direction by utilizing the peripheral speed difference of the roll group; The resin composition of the surface layer is melt-kneaded on at least one side of the longitudinally stretched film, laminated into a sheet, and then laterally stretched using a tenter, and then heat-treated and cooled. It can be obtained by:
• the stretching ratio is not particularly limited, and is appropriately selected depending on the purpose and the characteristics of the thermoplastic resin to be used.
• a propylene homopolymer or a copolymer thereof is used as the thermoplastic resin, it is about 1.2 to 12 times, preferably 2 to 10 times when stretched in one direction.
• the area ratio is 1.5 to 60 times, preferably 10 to 50 times.
• the area ratio is 1.5 to 20 times, preferably 4 to 12 times. Further, heat treatment at a high temperature is performed as necessary.
• the stretching temperature is 2 to 150 ° C lower than the melting point of the thermoplastic resin to be used. If the resin is a propylene homopolymer (melting point: 150 to 167 ° C), the stretching temperature is 120 to 1 ° C. 65 ° C, 80 to 120 ° C for high-density polyethylene (melting point 12 1 to 1334 ° C), 10 for polyethylene terephthalate (melting point 246 to 25 2 ° C) : ⁇ 1 15 ° C is preferred.
• the stretching speed is 20 to 35 Om / min.
• the thickness of the stretched thermoplastic resin finolem is from 20 to 350 / ⁇ , preferably from 35 to 300 / zm.
• the thermoplastic resin film of the present invention is preferably stretched in at least one direction.
• the void fraction calculated by the following equation is preferably 1 to 60%, more preferably 2 to 40%, and still more preferably 3 to 35%. If it is less than 1%, it is difficult to reduce the weight, and if it is more than 60%, there is a tendency that difficulties occur in the strength as a film.
• the opacity of the thermoplastic resin film is 10 to 100% (based on JIS-z-87222). Preferably, it is 10% or more and less than 70% for a translucent film, and 70 to 100% for an opaque film. If it is less than 10%, the void ratio of voids formed inside the film will be less than 1%, which tends to make it difficult to reduce the weight.
• the density of the thermoplastic resin film is preferably 0.65 to 1.10 gZcm 3 .
• the range is 0.90 to 1.10 gZcm 3 for a translucent film, and 0.65 to less than 0.90 gZ cm 3 for an opaque film.
• thermoplastic resin film examples include a treatment method selected from corona treatment, flame treatment, plasma treatment, glow discharge treatment, and ozone treatment. Corona treatment and flame treatment are preferred. The amount is for corona treatment
• FIG. 1 is a schematic cross-sectional view schematically showing one example of the coating layer of the thermoplastic resin film of the present invention.
• the coating layer is composed of a curable resin (A) having a pencil hardness of HB or higher according to JIS K-5600-5-4 and an olefin resin (B).
• the outer surface of the thermoplastic resin film contains projections derived from the olefin resin (B).
• the weight% ratio of the curable resin to the olefin resin is 5 to 99% by weight of the curable resin and 1 to 95% by weight of the olefin resin, preferably 10 to 95% by weight of the curable resin, and the olefin resin. 5 to 90 wt% is used, more preferably curable resin 30 to 95 wt 0/0, Orefin resin 5-70 wt% is used.
• the weight average particle diameter d (/ im) of the olefin resin (B) and the number ⁇ of protrusions derived from the olefin resin (B) per 10,000 zm 2 on the thermoplastic resin film are represented by the following formula. (1) is satisfied.
• the weight average particle size is 2 ⁇ m
• the number of particles per 10,000 m 2 area is 100/3 ⁇ n ⁇ 10,000 That is, the range 33 ⁇ n ⁇ 33 33 It will be an enclosure. If the number of particles is too small to satisfy the above formula, the scratch resistance deteriorates, and if the number of particles is too large, the adhesion of the ink decreases, which is not preferable.
• the curable resin used in the present invention has an elongation of 300 ° / 0 or less according to JI SK-7113, and preferably has an elongation of 200% or less. If the elongation exceeds 300%, the coating strength of the coating layer becomes weak, and the scratch resistance deteriorates.
• the curable resin is a curable resin having a pencil hardness of HB or higher in accordance with JIS-K-5600-5-4.
• thermosetting resin As such a curable resin, a thermosetting resin, an ultraviolet curable resin, and an electron beam curable resin can be used.
• thermosetting resin examples include a urea resin, a phenol resin, an unsaturated polyester resin, an epoxy resin, a silicone resin, a melamine resin, an alkyd resin, and a polyurethane resin.
• Examples of the ultraviolet curing resin and the electron beam curing resin include polyester acrylate resin, polyether acrylate resin, polyurethane acrylate resin, epoxy acrylate resin, and (meth) acrylate resin. it can.
• thermosetting resin is preferred from the viewpoint of good dispersion stability of the olefin resin, and a polyurethane resin is more preferably used.
• polyurethane resin a polyether urethane resin, a polyether ester urethane resin, or a polycarbonate urethane resin is used, and it is preferable to use a polyether / urethane resin or a polyether ester / urethane resin.
• the olefin resin used in the present invention must have a minimum film-forming temperature of 40 ° C or higher, preferably has a minimum film-forming temperature of 60 ° C or higher, and more preferably has a minimum film-forming temperature of 60 ° C or higher. Low film formation temperature is 80 ° C or higher. If the minimum film formation temperature is less than 40 ° C,
• the particle-based resin cannot maintain the shape of the particles after application and the scratch resistance is reduced.
• the shape of the olefin resin used in the present invention is not particularly limited as long as the intended effects of the present invention are exhibited, but it is preferable that the resin has a spherical or nearly spherical particle shape.
• the weight average particle size of the olefin resin is preferably from 0.1 to 10 ⁇ , and more preferably from 0.3 to 3 ⁇ . If the weight average particle diameter is less than 0.1 ⁇ m, the scratch resistance becomes poor, and if the weight average particle diameter exceeds 10 ⁇ m, the transferability of the ink decreases, which is not preferable.
• the olefin resin preferably contains an olefin copolymer to which a carboxylic acid and / or an anhydride thereof is bonded in order to impart adhesion to the base material and the curable resin (A).
• the acid content of the olefin copolymer to which a carboxylic acid or an anhydride thereof is bound is preferably 30% by weight or less, more preferably 20% by weight or less. Acid content is 30% by weight. If it exceeds / 0 , it is not preferable because the surface becomes sticky and cutting defects occur in the processing step.
• an antistatic agent as an additional component to the coating layer, it is possible to reduce the adhesion of dust and the trap due to charging during printing.
• a polymer type antistatic agent is preferable, and a cationic type, anion type, amphoteric type, nonionic type and the like can be used.
• the cationic type include those having an ammonium salt structure or a phosphonium salt structure.
• anion type examples include alkali metal salts such as sulfonic acid, phosphoric acid, and carboxylic acid; for example, alkali metal salts such as acrylic acid, methacrylic acid, and (anhydrous) maleic acid (eg, lithium salt, sodium salt, And the like having a structure in the molecular structure.
• alkali metal salts such as sulfonic acid, phosphoric acid, and carboxylic acid
• alkali metal salts such as acrylic acid, methacrylic acid, and (anhydrous) maleic acid (eg, lithium salt, sodium salt, And the like having a structure in the molecular structure.
• the amphoteric type contains both the cationic type and the anion type structures in the same molecule, and includes, for example, a betaine type.
• the nonionic type include an ethylene oxide polymer having an alkylene oxide structure and an ethylene oxide polymer.
• a polymer having a combined component in a molecular chain is exemplified.
• a polymer type antistatic agent having boron in its molecular structure can also be mentioned as an example.
• the coating layer may contain various known additives such as a light stabilizer such as a hindered amine light stabilizer, an antioxidant, and a flame retardant, if necessary.
• the coating layer may contain various known additives such as a light stabilizer such as a hindered amine light stabilizer, an antioxidant, an antistatic agent, and a flame retardant, if necessary. Various additives may be added to the coating agent and applied.
• the coating method of the coating agent is performed by a roll coater, blade coater, air knife coater, size press coater, gravure coater, reverse coater, die coater, spray coater, dipping, or the like.
• the coating amount of the coating agent is 0.05 to 20 g / m as solid content, and preferably 0.1 to: L 0 g Zm 2 .
• the coating may be performed on at least one side of the formed film, and may be performed in the film forming line or on another line already formed. If it involves a stretching step, it may be performed before or after that. If necessary, pass through a drying step to remove excess solvent.
• thermoplastic resin film obtained in this way is suitable for various types of printing, such as oxidation polymerization type (solvent type) offset printing, ultraviolet curing type offset printing, letterpress printing, gravure printing, and the like.
• oxidation polymerization type solvent type
• ultraviolet curing type offset printing ultraviolet curing type offset printing
• gravure printing gravure printing
• flexo printing ator press printing, etc., it is possible to print and print in sheet form or roll form.
• the thermoplastic resin film of the present invention can be used as a label by providing an adhesive layer on at least one side.
• the type and thickness (coating amount) of the pressure-sensitive adhesive layer to be provided can be variously selected depending on the type of the adherend, the environment in which it is used, the strength of adhesion, and the like.
• Typical water-based or solvent-based adhesives include rubber-based adhesives, acrylic-based adhesives, and silicone-based adhesives.
• Specific examples of the rubber-based adhesive include polyisobutylene rubber and butyl rubber. And a mixture thereof, or rosin abietic acid, terpene phenol copolymer, terpene Those containing a tackifier such as a polymer may be used.
• acrylic adhesives include 2-ethylhexyl acrylate “copolymer of n-butyl acrylate, 2-ethylhexyl acrylate / ethyl acrylate”, and methyl methacrylate copolymer. Having a glass transition point of 120 ° C. or lower.
• These synthetic polymer adhesives can be used in a form dispersed in water, such as an organic solvent solution or a disposable emulsion.
• an adhesive containing a pigment such as titanium white it is also possible to use an adhesive containing a pigment such as titanium white.
• the pressure-sensitive adhesive layer can be formed by applying the solution in a solution state on the bonding surface between the thermoplastic resin film and the release paper. Coating is performed by a low / coater, blade coater, bar coater, air knife coater, gravure coater, reverse coater, die coater, lip coater, spray coater, comma coater, etc. Or through a drying process, an adhesive layer is formed.
• the method of forming the pressure-sensitive adhesive layer is to apply a pressure-sensitive adhesive to release paper, dry if necessary, and laminate a thermoplastic resin film on the pressure-sensitive adhesive layer, but in some cases, It can also be formed by directly applying an adhesive to a thermoplastic resin film.
• the coating amount of the pressure-sensitive adhesive is not particularly limited, but is usually in the range of 3 to 60 g Zm 2 , preferably 10 to 40 g / m 2 in terms of solid content. Examples>
• MFR Melt index: 0.8 g / 10 min propylene homopolymer, 15 weight of heavy calcium carbonate having an average particle size of 1.5 ⁇ . / 0 composition containing the (E), was kneaded in 2 5 0 ° setting the extruder and C, extruded into a sheet form, a cooling device To obtain a non-stretched sheet. After heating the obtained sheet to a temperature of 140 ° C., it was stretched 5 times in the machine direction.
• (2) MF R is 1 0 GZL 0 minutes ethylene one propylene random copolymer 5 0 by weight 0/0 and carbonate Cal Shiumu 4 5 weight maleic acid-modified polypropylene 5% by weight and average particle diameter 1. 5 mu m % Of the composition (C) melt-kneaded by an extruder set at 240 ° C., 55% by weight of a propylene homopolymer having an MFR of 4 g / l 0 and 55% by weight and an average particle size A composition (D) containing 1.5% by weight of calcium carbonate (45% by weight) was melt-kneaded by another extruder set at 240 ° C., and the mixture was laminated in a die.
• a five-layer laminate (C) / (D) / (E) / (D) / (5) is extruded on both sides of the 5-fold stretched sheet obtained in (1) above so that C) is on the outside. C).
• this five-layer laminate After heating this five-layer laminate to 155 ° C, it was stretched by a factor of 8.0 in the transverse direction to form a five-layer laminate film (thickness: 4 ⁇ 2 8 6 ⁇ / 28 im / A ⁇ ) was obtained.
• a five-layer laminate was obtained in the same manner as in Production Example 1, except that the composition of (C) in Production Example 1 was changed to a propylene homopolymer having an MFR of 4 gZl0 min.
• the porosity of the base material thus obtained was 32%, the density was 0.78 gZm 3 , the opacity was 93%, and the Beck smoothness was 2000 seconds.
• Melt flow rate (MFR) 0.8 gZl A mixture of 72% by weight of propylene homopolymer in 0 minutes and 8% by weight of high-density polyethylene was added to a charcoal with an average particle size of 1.5 ⁇ .
• Composition (D) was prepared by blending 20% by weight of calcium acid.
• a composition (C) was prepared by blending a propylene homopolymer having an MFR of 4 g / 10 min.
• compositions (C) and (D) were melt-kneaded in separate extruders set at 270 ° C, respectively, and then (C) / (D) / (C) Were laminated and co-extruded into a sheet from one die, and cooled by a cooling device to obtain a non-stretched sheet. After heating this sheet to 155 ° C, it was stretched 5 times in the machine direction by utilizing the peripheral speed difference of the roll group.
• the film is stretched 7.5 times using a tenter in the horizontal direction, and annealed at 163 ° C, and the three-layer film is formed. Obtained.
• the surface of this three-layer laminated film is subjected to corona discharge treatment, and a three-layered multilayer structure of (C) / (D) / (C) [thickness of each film is 5 ⁇ / 50 ⁇ / 5 ⁇ m]
• a resin stretched film was obtained.
• the porosity of the base material thus obtained was 21%, the density was 0.80 g / m 3 , the opacity was 90%, and the Bekk smoothness was 20000 seconds.
• Melt flow rate (MFR) 0.8 gZ 10 minutes of a mixture of 72% by weight of propylene homopolymer and 8% by weight of high-density polyethylene mixed with 20% by weight of calcium carbonate having an average particle size of 1.5 ⁇
• the composition (C) was prepared by blending. Apart from this, Micromax FR is l O GZL O content of propylene homopolymer copolymer 5 0 wt% of maleic acid-modified polypropylene 5 weight 0/0 and the average particle diameter 1. 5 tm calcium carbonate 4 5 weight 0 / 0 was prepared as a composition (D).
• compositions (C) and (D) were melt-kneaded in separate extruders set at 270 ° C., and the mixture was melted and kneaded from a single die into (C) / (D) / ( C) was co-extruded into a sheet and cooled by a cooling device to obtain a non-stretched sheet. After heating this sheet to 130 ° C, it was stretched 5 times in the longitudinal direction by utilizing the difference in peripheral speed of the roll group, and was annealed at 145 ° C to obtain a three-layer film.
• the surface of the three-layer film is subjected to corona discharge treatment, and (C) / (D) / (C) [The thickness of each film is 15 ⁇ m / 100 ⁇ m / 15 / / m] three-layer stretched resin film Got.
• the porosity of the substrate thus obtained was 30%, the density was 0.88 g / m 3 , the opacity was 91%, and the Bekk smoothness was 1600 seconds.
• Both surfaces of the substrate (P-1) of Production Example 1 of the above-mentioned substrate resin film were subjected to a line speed of about 30 mZ and an applied energy density of 10 using a corona discharge treatment machine AG I-043D manufactured by Kasuga Electric Co., Ltd. Surface treatment was performed at OW ⁇ min / m 2 . Then, 74% by weight of thermosetting polyester urethane resin “HUX-522” (trade name, manufactured by Asahi Denka Co., Ltd.) and polyethylene resin emulsion “W700” (trade name, manufactured by Mitsui Chemicals, Inc.) Is coated on both sides using a roll coater, dried at a temperature of about 65 ° C for several tens of seconds and wound up. The coating amount is 0.15 g / m 2 of surface-modified synthetic paper was obtained. The synthetic paper was evaluated for suitability for offset printing (ink transferability, adhesion, and scratch resistance) by the following method.
• the transferability, adhesion, and scratch resistance of the ink were evaluated by the following measurement methods.
• the obtained synthetic paper is oxidized and polymerized ink (Varius G, Ink, Indigo, Crimson, Yellow) manufactured by Mitsubishi Heavy Industries, Ltd. with Diamond OF-4 (Kikusoji) manufactured by Dainippon Ink and Chemicals, Inc. Perform offset printing of the pattern using (4 colors), measure the ink transfer density, and visually observe the transfer state of the ink on the entire surface for any transfer defects such as streaks and white spots. The evaluation was made in five stages.
• Example 1 was at a level of 5. The results are shown in Table 1.
• the peeled portion was about 25 to 50% (some problem in practical use).
• the peeled portion was 50% or more (problematic in practice).
• Example 1 was at a level of 5. The results are shown in Table 1.
• the obtained synthetic paper is oxidized and polymerized ink (Varius G, Ink, Indigo, Crimson, Yellow) manufactured by Mitsubishi Heavy Industries, Ltd. with Diamond OF-4 (Kikusoji) manufactured by Dainippon Ink and Chemicals, Inc. 4 colors), and store them for one week while stacking them. After that, 50% halftone dot of black ink, 100% halftone dot of black ink, and black ink The 400% dot area where the yellow ink was superimposed was rubbed with a nail and the degree of peeling of the ink was visually observed, and the scratch resistance was evaluated according to the following five levels.
• the peeled portion was about 25 to 50% (practically a little problematic).
• the peeled portion was 50% or more (problematic in practice).
• Example 1 was at a level of 5. The results are shown in Table 1.
• a film was prepared and evaluated in the same manner as in Example 1 except that the amount and type of urethane resin in the coating agent were changed. The results are shown in Table 1.
• Example 5 A film was prepared and evaluated in the same manner as in Example 1, except that the amount and type of the olefin resin in the coating agent were changed. The results are shown in Table 1.
• Example 1 Except for changing the type of the base resin sheet, the same operation as in Example 1 was performed, and a film was prepared and evaluated. The results are shown in Table 1.
• a film was prepared and evaluated in the same manner as in Example 1 except that only the urethane resin was used as the coating agent. The results are shown in Table 1.
• a film was prepared and evaluated in the same manner as in Example 1 except that only the coating resin was used as the olefin resin. The results are shown in Table 1.
• a film was prepared and evaluated in the same manner as in Example 1 except that no coating agent was applied. The results are shown in Table 1.
• a film was prepared and evaluated in the same manner as in Example 1 except that the type of urethane resin in the coating agent was changed. The results are shown in Table 1.
• A-1 Thermosetting polyester urethane resin "HUX-522" (Asahi Denka Co., Ltd., trade name) Pencil hardness 2 H
• A-2 Thermosetting polyester ether urethane resin "HUX-523" (trade name, manufactured by Asahi Denka Co., Ltd.) Pencil hardness 4H
• thermoplastic resin film according to the present invention is an oxidative polymerization type ink, an ultraviolet ray.
• thermoplastic resin film of the present invention is used for printed matter requiring water resistance, such as a label adhered to an outdoor booster or a container for frozen food, and is capable of printing gravure, flexo, letter press, offset, etc. And an expressive seal

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